Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4202—Two or more polyesters of different physical or chemical nature
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters

Definitions

• the present invention relates to a process for the preparation of a clear coat layer of an automotive OEM (original equipment manufacture) multi-layer coating making use of a two-component polyurethane clear coat composition.
• Two-component polyurethane coating compositions are coating compositions that crosslink by formation of urethane bonds as a result of the addition reaction between the hydroxyl groups of a hydroxyl-functional binder component and the free isocyanate groups of a polyisocyanate crosslinker component.
• the hydroxyl-functional binder component and the polyisocyanate crosslinker component are stored separately from one another before being mixed to form the two-component polyurethane coating composition.
• two-component polyurethane coating compositions are prepared just prior to their application by mixing a hydroxyl-functional binder component with a polyisocyanate crosslinker component.
• Typical mixing equipment for two-component coatings present in automotive OEM coating plants are static mixers such as, in particular, Kenics mixers.
• the substrates to be spray coated are supplied in succession to the spray application apparatus, for example, by using an automatic conveying apparatus, for example, a conveyor belt.
• the spray application itself is effected while the individual substrate to be spray coated and/or the spray application apparatus are in motion.
• the spray application process in automotive OEM coating plants is distinguished by breaks or interruptions which do not only occur between two individual substrates, i.e. not only in the time period after the spray coating of a substrate has been finished and before that of the following substrate is started, but even in the course of the spray coating of an individual substrate.
• Such breaks or interruptions may happen either unintentionally or deliberately and they may differ in duration. For example, they may take 0.5 seconds to 15 minutes. During such breaks or interruptions no coating material is sprayed and, after the break has ended, spray coating is taken up again at that position on the substrate surface where it had been interrupted when the break began.
• the present invention relates to a process for the preparation of an outer clear coat layer of an automotive OEM multi-layer coating comprising the steps:
• step (1) of the process of the present invention an automotive substrate to be OEM clear coated is provided.
• autonomous substrate to be OEM clear coated refers to an automotive substrate that lacks a clear coat, or more precisely, an original clear coat as opposed to, for example, a repair clear coat.
• Automotive substrates to be OEM clear coated include in particular precoated automotive bodies and precoated automotive body metal or plastic parts, the precoatings in each case lacking a final outer clear coat layer, as explained in the preceding paragraph.
• the precoatings themselves comprise an outer pigmented coating layer which determines the color of the finished automotive substrate.
• automotive bodies include truck and vehicle bodies, for example, passenger car bodies and van bodies.
• automotive body metal or plastic parts include doors, bonnets, boot lids, hatchbacks, wings, spoilers, bumpers, collision protection strips, side trim, sills, mirror housings, door handles and hubcaps.
• finished automotive substrate refers to an automotive substrate provided with the automotive OEM multi-layer coating which is the result of the process of the present invention, i.e. the automotive OEM multi-layer coating including the thermally cured outer clear coat layer obtained on completion of step (6) of the process of the present invention.
• the color-determining precoating may be a single- or multi-layer precoating which in any case still needs a final outer clear coat layer.
• the precoating or, in particular, the outer layer of the precoating may be already cured or still uncured. In the latter case it will be jointly thermally cured together with the clear coat spray-applied from the two-component polyurethane clear coat composition.
• the precoated automotive bodies are automotive bodies which have already been provided with a conventional automotive OEM multi-layer coating except for the final outer clear coat layer.
• the precoating may comprise only one coating layer.
• the precoatings are precoatings which are applied in the context of an automotive OEM coating process, i.e. generally in the context of an industrial automotive OEM mass production coating process.
• the precoating on the automotive substrate comprises an outer pigmented coating layer which determines the color of the finished automotive substrate.
• such color-determining coating layers which require an outer clear coat layer are typically applied from solventborne or waterborne pigmented base coats.
• precoatings lacking an outer clear coat layer include (i) a multi-layer coating comprising a plastics primer layer and an outer base coat layer, in particular, a multi-layer coating consisting of a plastics primer layer and an outer base coat layer and (ii) a single-layer coating in the form of a base coat layer.
• step (2) of the process of the present invention there is provided a binder component having a solids content of 42 to 50 wt.-% comprising at least one hydroxyl-functional binder and a volatile organic content of 50 to 58 wt.-%, wherein the sum of the wt.-% totals 100 wt.-%.
• binder solids and “crosslinker solids” are used. They refer to the solids contribution of the coating binders (binder solids) and the solids contribution of the crosslinkers (crosslinker solids) contained in the two-component polyurethane clear coat composition. Binder solids and crosslinker solids together form the resin solids of the two-component polyurethane clear coat composition.
• the resin solids together with any further non-volatile constituents that may be present in the two-component polyurethane clear coat composition form the solids of the two-component polyurethane clear coat composition. Examples of such further non-volatile constituents include non-volatile additives and transparent fillers (transparent extender pigments). To avoid misunderstandings, the solids content of the two-component polyurethane clear coat composition shall not be confused with the solids content of the binder component or of the polyisocyanate crosslinker component.
• volatile organic content refers to the sum of all volatile organic constituents, i.e, the sum of organic solvents and, if present, volatile organic additives.
• the solids content of the binder component has a hydroxyl number originating from the at least one hydroxyl-functional binder of, for example, 110 to 160 mg KOH/g.
• Both, the binder component as well as the two-component polyurethane clear coat composition comprise one and the same binder solids.
• the binder solids comprise the at least one hydroxyl-functional binder and the optionally present further binders other than hydroxyl-functional binders.
• the binder solids consist of one or more hydroxyl-functional binders.
• Hydroxyl-functional binders and methods for their preparation are known to the person skilled in the art of paints and coatings. Examples include hydroxyl-functional resins like polyurethane resins, (meth)acrylic copolymer resins and polyester resins, but also polymer hybrid resins, wherein two or more of said resin types bound by covalent bonds or in the form of interpenetrating resin molecules are present.
• (Meth)acryl or (meth)acrylic is to be understood, both here and in the following, as acryl and/or methacryl or as acrylic and/or methacrylic.
• hydroxyl-functional (meth)acrylic copolymer resins and polyester resins are preferred as hydroxyl-functional binders in the binder component provided in step (2) of the process of the present invention.
• the hydroxyl-functional binders are oligomeric or polymeric compounds with a number-average molar mass (Mn) in the range of, for example, 500 to 5000, preferably 1000 to 3000. Their hydroxyl numbers are in the range of, for example, 100 to 300 mg KOH/g.
• binder resins without functional groups or with functional groups other than hydroxyl groups.
• resin types are the same as those mentioned above for the hydroxyl-functional binders.
• the further binders belong to the binder solids content of the binder component and they may form up to 10 wt.-% of the binder solids content. It is however preferred that the binder component contains no further binders other than hydroxyl-functional binders.
• crosslinkers other than free polyisocyanate crosslinkers which may be contained in the binder component include reversibly blocked polyisocyanate crosslinkers and aminoplast resins, in particular, melamine resins.
• Such crosslinkers do not belong to the binder solids content of the binder component but together with the free polyisocyanates of the polyisocyanate crosslinker component they form the crosslinker solids of the two-component polyurethane clear coat composition.
• the crosslinkers other than free polyisocyanate crosslinkers may form up to 40 wt.-% of the crosslinker solids of the two-component polyurethane clear coat composition.
• the crosslinker solids of the two-component polyurethane clear coat composition consist of the at least one polyisocyanate of the 1,6-hexane diisocyanate isocyanurate type and the optionally present at least one polyisocyanate of the isophorone diisocyanate isocyanurate type.
• the process of the present invention is of particular value, in case the binder component comprises melamine resin, in particular, in a proportion corresponding to 20 to 40 wt.-% of the crosslinker solids of the two-component polyurethane clear coat composition.
• the reason is that such two-component polyurethane clear coat compositions containing melamine resin and prepared by static mixing are especially susceptible to interruptions of or breaks during the spray-application and the disadvantages associated therewith regarding formation of optical surface defects, as explained in the section "Background of the Invention" above.
• the binder component contains one or more organic solvents in a total amount of, for example, 48 to 58 wt.-%.
• organic solvents include monohydric or polyhydric alcohols, for example, propanol, butanol, hexanol; glycol ethers or esters, for example, diethylene glycol dialkylethers, dipropylene glycol dialkylethers, in each case with C1- to C6-alkyl, ethoxypropanol, butylglycol; glycols, for example, propylene glycol and oligomers thereof; glycol ether esters, for example, ethyl glycol acetate, butyl glycol acetate, 3-methoxy-n-butyl acetate, butyl diglycol acetate, methoxypropyl acetate; N-methylpyrrolidone and ketones, such as, methyl ethyl ketone, acetone, cyclohexanone;
• Additives may be present in the binder component in a total amount of, for example, up to 5 wt.-%.
• paint additives such as leveling agents, wetting agents, dyes, light stabilizers, antioxidants, rheology control agents, anti-settling agents, antifoaming agents, adhesion-promoting substances, catalysts.
• transparent fillers examples include silica.
• step (3) of the process of the present invention there is provided a polyisocyanate crosslinker component having a solids content of 66 to 70 wt.-% and a volatile organic content of 30 to 34 wt.-%, wherein the sum of the wt.-% totals 100 wt.-%.
• the solids content of the polyisocyanate crosslinker component comprises a free polyisocyanate solids content consisting of 75 to 100 wt.-% of at least one polyisocyanate of the 1,6-hexane diisocyanate isocyanurate type and of 0 to 25 wt.-% of at least one polyisocyanate of the isophorone diisocyanate isocyanurate type, wherein the sum of the wt.-% totals 100 wt.-%.
• the solids content of the polyisocyanate crosslinker component may further comprise one or more non-volatile additives as optional constituents. If the polyisocyanate crosslinker component contains no non-volatile additives, the solids content of the polyisocyanate crosslinker component consists of the free polyisocyanate solids content.
• polyisocyanate of the 1,6-hexane diisocyanate isocyanurate type is used. It means trimerization products of 1,6-hexane diisocyanate, for example, trimeric 1,6-hexane diisocyanate (1,6-hexane diisocyanate isocyanurate).
• polyisocyanate of the isophorone diisocyanate isocyanurate type is used. It means trimerization products of isophorone diisocyanate, for example, trimeric isophorone diisocyanate (isophorone diisocyanate isocyanurate).
• the volatile organic content of the polyisocyanate crosslinker component consists of one or more organic solvents inert towards free isocyanate groups and, optionally, of up to 2 wt.-% of one or more volatile organic additives.
• organic solvents which are inert towards free isocyanate groups include, for example, glycol ether esters, such as, ethyl glycol acetate, butyl glycol acetate, 3-methoxy-n-butyl acetate, butyl diglycol acetate, methoxypropyl acetate; ketones, such as, methyl ethyl ketone, cyclohexanone; esters, such as, butyl acetate, isobutyl acetate, amyl acetate; aromatic or aliphatic hydrocarbons, for example, toluene, xylene or linear or branched, aliphatic C6- to C12-hydrocarbons.
• glycol ether esters such as, ethyl glycol acetate, butyl glycol acetate, 3-methoxy-n-butyl acetate, butyl diglycol acetate, methoxypropyl acetate
• ketones such as
• the polyisocyanate crosslinker component may contain one or more additives in a total proportion of, for example, up to 5 wt.-%.
• additives include paint additives such as leveling agents, wetting agents, dyes, light stabilizers, antioxidants, adhesion-promoting substances, catalysts.
• the binder component and the polyisocyanate crosslinker component are stored separately from one another in order to prevent a premature cross-linking reaction until step (4) of the process of the present invention is carried out.
• step (4) of the process of the present invention a two-component polyurethane clear coat composition is prepared by static mixing the binder component provided in step (2) and the polyisocyanate crosslinker component provided in step (3).
• Mixing is carried out in a specified ratio, for example, in a ratio corresponding to a 1:0.7 to 1:2 stoichiometry between the hydroxyl groups originating from the binder solids of the binder component and the free isocyanate groups originating from the polyisocyanate crosslinker component.
• the two components are mixed together making use of a static mixer, for example, a conventional static mixer such as, in particular, a Kenics mixer.
• Kenics mixers are static mixers typically used for automotive OEM industrial production line coating and they have a length of, for example, 40 to 200 mm.
• the static mixing allows for a continuous mixing of the two components to be mixed shortly before the two-component polyurethane clear coat composition is spray-applied during step (5) of the process of the present invention.
• the two-component polyurethane clear coat composition so prepared leaves the static mixer and it is fed to the one or more spray-application devices.
• the two-component polyurethane clear coat composition has a solids content in the range of, for example, 45 to 60 wt.-%.
• the volatile content of the two-component polyurethane clear coat composition is formed by (i) the organic solvent(s) originating from the binder component, (ii) the organic solvent(s) originating from the polyisocyanate crosslinker component and (iii) optionally present volatile organic additives.
• step (5) of the process of the present invention the two-component polyurethane clear coat composition is spray-applied on the automotive substrate to be OEM clear coated.
• the spray-application process is performed with one or more interruptions of in each case, for example, 0.5 seconds to 15 minutes with taking the spray-application up again at that position on the automotive substrate surface where it had been interrupted before.
• Spray-application is carried out by conventional spray-application devices which are generally operated with electrostatic assistance. Examples of spray-application devices which are particularly suitable are high-speed rotary atomizers.
• the two-component polyurethane clear coat composition is spray-applied in a dry film thickness in the range of, for example, 20 to 60 ⁇ m. Then, preferably after a brief flash-off phase of, for example, 30 seconds to 10 minutes at an air temperature of 20 to 25°C, the clear coat layer is thermally cured in step (6) of the process of the present invention.
• Thermal curing is preferably carried out by baking. Thermal curing takes, for example, 20 to 30 minutes and is carried out at object temperatures in the range of, for example, 80 to 160°C.
• the process of the present invention is carried out in the context of an industrial automotive OEM mass production coating process, in particular, i.e. in an industrial automotive OEM painting facility.
• a binder component (clear coat base) was prepared from the following constituents:
• a two-component polyurethane clear coat composition was prepared from the binder component from Example 1.1) and the polyisocyanate crosslinker component from Example 1.2). Both components were dosed over the Kenics mixer in a mixing ratio of 3 pbw of binder component : 1 pbw of polyisocyanate crosslinker component.
• the two-component polyurethane clear coat composition so prepared exiting the Kenics mixer was directly fed to a high-speed rotary atomizer and spray-applied in 45 ⁇ m dry film thickness onto a 30cm x 60cm automotive body steel test panel provided with electrocoat primer, primer surfacer and black water-borne base coat (predried). Application was performed following a spray path with rectangle profile. After 5 minutes flashing off at room temperature the clear coat was bake cured for 20 minutes at 140 °C (object temperature).
• Example 1.3) was repeated with the difference that the spray-application was interrupted for 20 seconds when the high-speed rotary atomizer reached the middle of the test panel's surface, i.e. after the 20 seconds interruption period the spray application was taken up again at that same position on the panel's surface.
• Example 1.4 was repeated with the difference that a mixing ratio of 2.5 pbw of binder component: 1 pbw of polyisocyanate crosslinker component was used.
• Example 1.3 was repeated with the difference that a different polyisocyanate component prepared by dissolving 80 pbw of Desmodur® N 3300 in 20 pbw of an organic solvent mixture (80 pbw Solvesso TM 100 and 20 pbw butyl acetate) was used.
• Example 1.4 was repeated with the difference that a different polyisocyanate component prepared by dissolving 80 pbw of Desmodur® N 3300 in 20 pbw of an organic solvent mixture (80 pbw Solvesso TM 100 and 20 pbw butyl acetate) was used.
• the multi-layer coatings obtained were tested for their visual impression. DOI (distinctness of image), long wave (LW), short wave (SW) and dullness (DU) were determined using the measuring device Wavescan DOI from BYK-Gardner. In case of examples 1.4), 2) and 4) the testing was made in a circle (10cm in diameter) around the middle of the test panel where the clear coat application had been interrupted for 20 seconds. Table 1 shows the results that were obtained.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Paints Or Removers (AREA)

Applications Claiming Priority (1)

Publications (2)

Family

ID=42263910

Family Applications (1)

Country Status (3)

Cited By (1)

Citations (4)

Family Cites Families (5)

• 2010
  • 2010-02-19 US US12/708,691 patent/US8361558B2/en active Active
  • 2010-03-02 EP EP10155237A patent/EP2239289B1/fr active Active
  • 2010-03-02 ES ES10155237T patent/ES2401699T3/es active Active

Patent Citations (4)

Also Published As

Similar Documents

Legal Events